CN109300698A - A kind of lithium-ion capacitor and preparation method thereof - Google Patents
A kind of lithium-ion capacitor and preparation method thereof Download PDFInfo
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- CN109300698A CN109300698A CN201811136733.2A CN201811136733A CN109300698A CN 109300698 A CN109300698 A CN 109300698A CN 201811136733 A CN201811136733 A CN 201811136733A CN 109300698 A CN109300698 A CN 109300698A
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- Prior art keywords
- pole piece
- lithium
- anode pole
- anode
- ion capacitor
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Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 62
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000003990 capacitor Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 45
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000011230 binding agent Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000003475 lamination Methods 0.000 claims abstract description 20
- 239000006258 conductive agent Substances 0.000 claims abstract description 18
- 239000011149 active material Substances 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000007774 positive electrode material Substances 0.000 claims abstract description 8
- 239000012530 fluid Substances 0.000 claims abstract description 7
- 238000002347 injection Methods 0.000 claims abstract description 7
- 239000007924 injection Substances 0.000 claims abstract description 7
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- 230000004913 activation Effects 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 38
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 16
- 239000005030 aluminium foil Substances 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000007773 negative electrode material Substances 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 12
- 239000002041 carbon nanotube Substances 0.000 claims description 12
- 239000011889 copper foil Substances 0.000 claims description 12
- 238000003466 welding Methods 0.000 claims description 12
- 238000005520 cutting process Methods 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000011888 foil Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 6
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 6
- 239000004816 latex Substances 0.000 claims description 6
- 229920000126 latex Polymers 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 238000004513 sizing Methods 0.000 claims description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 238000010586 diagram Methods 0.000 claims description 3
- 230000005518 electrochemistry Effects 0.000 claims description 3
- 239000011267 electrode slurry Substances 0.000 claims description 3
- 238000005538 encapsulation Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 239000002985 plastic film Substances 0.000 claims description 3
- 229920006255 plastic film Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- AWKHTBXFNVGFRX-UHFFFAOYSA-K iron(2+);manganese(2+);phosphate Chemical compound [Mn+2].[Fe+2].[O-]P([O-])([O-])=O AWKHTBXFNVGFRX-UHFFFAOYSA-K 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 2
- 229910001453 nickel ion Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- MOLYXOOGDFTUJT-UHFFFAOYSA-L [Li].[Mn](=O)(=O)(O)O.[Co] Chemical compound [Li].[Mn](=O)(=O)(O)O.[Co] MOLYXOOGDFTUJT-UHFFFAOYSA-L 0.000 claims 1
- 239000006183 anode active material Substances 0.000 claims 1
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 claims 1
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 claims 1
- 239000006182 cathode active material Substances 0.000 claims 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004804 winding Methods 0.000 abstract description 2
- 239000002033 PVDF binder Substances 0.000 description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 description 8
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of lithium-ion capacitors and preparation method thereof, including anode pole piece, cathode pole piece, diaphragm, electrolyte and shell, the anode pole piece includes anode pole piece I, anode pole piece II, wherein anode pole piece I is to provide lithium source electrode, anode pole piece I includes collector, binder, conductive agent, positive electrode active materials I, anode pole piece II is with capacitive property electrode, anode pole piece II includes collector, binder, conductive agent, active material, lamination or winding assembling, weld, enter shell, lithium-ion capacitor is made in fluid injection, activation procedure.The lithium-ion capacitor making technology process of the invention and lithium ion battery process flow are about the same, safety and it is simple, feasibility is strong, easy realization industrial volume production, there is biggish application value.
Description
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of lithium-ion capacitor and preparation method thereof.
Background technique
As fossil fuel constantly consumes and environmental problem is got worse, tap a new source of energy for human survival sustainable development
Exhibition has great importance.As a kind of energy storage device, they are the passes to tap a new source of energy for lithium ion battery and supercapacitor
One of key factor.Lithium ion battery have high-energy density, high voltage, low self-discharge, memory-less effect, long circulation life it is excellent
Point, but power density is low；Supercapacitor is up to ten thousand secondary almost unattenuated with high power density, cycle-index, but energy density
It is low.Lithium-ion capacitor is a kind of electrochemical energy storing device for mutually merging both lithium ion battery and supercapacitor, simultaneous
The characteristics of for lithium ion battery high-energy density, supercapacitor high power density and long circulation life, in new energy vapour
The fields such as vehicle, urban track traffic, cold-starting have biggish application prospect.
Currently, lithium-ion capacitor is mainly that anode uses the nano material with large specific surface area to be used as active material
Material forms electric double layer with electrolyte, has performance of the supercapacitor；Cathode is using the carbon material of embedding lithium as active material, energy
Lithium abjection and insertion are enough formed, there is performance of lithium ion battery.Since lithium metal activity is larger, the oxygen gas and water that is easy in air
It chemically reacts, it is dangerous, so in the actual production process, making embedding lithium carbon material with larger difficulty.Patent
CN201510130056.3 announces a kind of capacitor of lithium ion battery cathode, and the method for making embedding cathode of lithium is using lithium powder is equal
Even spreading obtains embedding cathode of lithium on cathode pole piece by way of roll-in, this method the disadvantage is that, lithium powder activity is larger,
Easily react, it is dangerous, while in operating process, lithium powder disperses in air, to be easily inhaled into, staff's life is threatened,
So it is low using the method feasibility, it is unfavorable for industrial volume production.Patent CN201610072072.6 discloses a kind of lithium ion
Capacitor and preparation method thereof, the patent are used as auxiliary electrode using lithium metal, in cathode formation intercalation materials of li ions, but lithium metal
It is active big, it is unfavorable for operating, while auxiliary electrode, in the embedding lithium of cathode and uneven, this also will affect lithium-ion capacitor
Energy.Patent CN201210332874.8 discloses lithium ion super capacitor and its assembling side of a kind of high-energy high-power density
Method, the patent mixed in pole piece manufacturing process lithium metal or this electrode slice place metal lithium sheet, although in this way can with embedding lithium,
It is more difficult in actual production operating process but due to the activity of lithium metal.
Therefore, a kind of new lithium-ion capacitor and preparation method thereof is developed, not only there is urgent researching value, it may have
Good economic benefit and commercial application potentiality, where this power exactly of the invention being accomplished and basis.
Summary of the invention
In order to overcome the defect of the prior art as indicated above, the present inventor has made intensive studies this, is paying
After a large amount of creative works, so as to complete the present invention.
Specifically, the technical problems to be solved by the present invention are: provide a kind of lithium-ion capacitor and preparation method thereof,
It is difficult to solve the problems, such as to make embedding lithium titanate cathode material at present.
In order to solve the above technical problems, the technical scheme is that
In a first aspect, the present invention provides a kind of lithium-ion capacitor, including anode pole piece, cathode pole piece, diaphragm, electrolysis
Liquid and shell, the anode pole piece include anode pole piece I, anode pole piece II, and wherein anode pole piece I is to provide lithium source electrode, just
Pole pole piece I includes collector, binder, conductive agent, positive electrode active materials I, and anode pole piece II is with capacitive property electrode, just
Pole pole piece II includes collector, and binder, conductive agent, active material, cathode pole piece is to be electrolysed with battery performance battery performance,
Cathode pole piece includes collector, binder, conductive agent, active material, passes through ingredient, coating, roll-in, cutting system with superior pole piece
It is standby, and successively folded in a manner of diaphragm, anode pole piece I, diaphragm, cathode pole piece, diaphragm, anode pole piece II, diaphragm, cathode pole piece
Piece or winding assembling, weld, enter shell, lithium-ion capacitor is made in fluid injection, activation procedure.
In the present invention, as a kind of perferred technical scheme, the anode pole piece I by collector, positive electrode active materials, lead
Electric agent, binder composition, wherein positive electrode active materials are preferred lithium nickelate, cobalt acid lithium, LiMn2O4, ternary nickle cobalt lithium manganate, three
One of first nickel cobalt lithium aluminate, ferrate-lithium, LiFePO4, iron manganese phosphate for lithium, nickel ion doped, lithium-rich manganese base material, it is described
Positive electrode active materials, conductive agent, binder ratio be 98~90:6~1.0:4~0.8.
In the present invention, as a kind of perferred technical scheme, the anode pole piece II is by collector, active material, conduction
Agent, binder composition, wherein active material is one of nano-carbon materials such as graphene, active carbon, porous carbon, active material
Material, conductive agent, binder ratio be 97~90:7.5~1.5:3.5~0.8.
In the present invention, as a kind of perferred technical scheme, the plus plate current-collecting body is non-porous or has hole aluminium foil, with a thickness of
10 μm~20 μm.
In the present invention, as a kind of perferred technical scheme, the cathode pole piece by collector, negative electrode active material, lead
Electric agent, binder composition, wherein negative electrode active material be graphite (artificial graphite, natural graphite), carbonaceous mesophase spherules, hard carbon,
One of negative electrode materials such as soft carbon, silicon-carbon/silicon oxygen are a variety of, the percentage composition of negative electrode active material, conductive agent, binder
Range is respectively 97~92:5~0.5:3.5~0.8.
In the present invention, as a kind of perferred technical scheme, the negative current collector be micropore copper foil, with a thickness of 6 μm~
16 μm, porosity is 10%~70%, and pore size is 20 μm~130 μm.
In the present invention, as a kind of perferred technical scheme, the conductive agent that the positive and negative electrode pole piece uses is conductive carbon
Black, electrically conductive graphite, carbon fiber, carbon nanotube, graphene and its hybrid conductive slurry etc. are one such or a variety of.
In the present invention, as a kind of perferred technical scheme, the binder is polytetrafluoroethylene (PTFE), Kynoar, carboxylic
Methylcellulose receives, poly- butadiene-styrene latex etc. is one such or a variety of.
In the present invention, as a kind of perferred technical scheme, the diaphragm is polyethylene, polypropylene, polyethylene/poly- third
One of alkene/polyethylene diagrams.
In the present invention, as a kind of perferred technical scheme, the electrolyte used in fluid injection process for organic electrolyte,
Middle organic solvent is one of ethylene carbonate, propene carbonate, methyl ethyl carbonate, methyl carbonate, ethyl carbonate etc. or more
Kind, electrolyte is one of lithium hexafluoro phosphate, LiBF4, lithium perchlorate, di-oxalate lithium borate etc. or a variety of.
In a first aspect, including the following steps: the present invention provides the preparation method of lithium-ion capacitor
(1) anode pole piece I makes:
By each substance by weight percent than uniformly mixing, stable slurry is formed；Prepared anode sizing agent is uniformly applied
For cloth in aluminium foil tow sides, aluminium foil both sides reserve sky foil as pole-piece pole-ear position, tab welding are used for, after roll-in, cross cutting
Positive plate is made, made positive plate is placed and is saved under vacuum condition (- 0.07~-0.1MPa), for use；
(2) anode pole piece II makes:
By each substance by weight percent than uniformly mixing, stable slurry is formed；Prepared anode sizing agent is uniformly applied
For cloth in aluminium foil tow sides, aluminium foil both sides reserve sky foil as pole-piece pole-ear position, tab welding are used for, after roll-in, cross cutting
Positive plate is made, made positive plate is placed and is saved under vacuum condition, for use；
(3) cathode pole piece makes:
By each substance by weight percent than uniformly mixing, stable slurry is formed；Prepared negative electrode slurry is uniformly applied
For cloth in micropore copper foil tow sides, copper foil both sides reserve sky foil as pole-piece pole-ear position, are used for tab welding, pass through roll-in, mould
Negative electrode tab is made after cutting, made negative electrode tab is placed and is saved under vacuum condition, for use；
(4) lithium-ion capacitor assembles:
It is assembled by the way of lamination, successively with diaphragm, anode pole piece I, diaphragm, cathode pole piece, diaphragm, anode pole piece
II, diaphragm, cathode pole piece, diaphragm sequence lamination be fabricated to naked battery core, after short-circuit test, through tab welding, aluminum plastic film encapsulation,
Roasting procedure (baking temperature is 80 DEG C, for 24 hours)；Fluid injection；Constant-current charge (constant-current charge is carried out to anode pole piece I and cathode pole piece
Electric current 0.1C, blanking voltage 4.15V), the pre- embedding lithium of electrochemistry is carried out, after the molding of two envelopes, anode pole piece II and cathode pole piece shape
At lithium-ion capacitor.
After above-mentioned technical proposal, the beneficial effects of the present invention are:
This patent uses two kinds of anode pole pieces (anode pole piece I, anode pole piece II), and negative electrode material is coated in micropore copper foil
On, and lamination or volume in a manner of anode pole piece I, diaphragm, cathode pole piece, diaphragm, anode pole piece II, diaphragm, cathode pole piece
Around assembling.First using low current by anode pole piece I and cathode pole piece electricizing activation, the lithium of anode pole piece I is embedded into cathode pole piece,
Form embedding lithium titanate cathode material；Anode pole piece II is connect with cathode again, since cathode is coated on micropore copper foil, lithium can be negative
In the active material of pole two sides migrate, thus with anode pole piece II and form lithium-ion capacitor.
The present invention makes full use of the characteristics of micropore copper foil, and lithium can be certainly in insertion and abjection negative electrode active material process
It is migrated by ground on the two sides of cathode pole piece, lithium is embedded in negative electrode material by way of electricizing activation, it is equal to form embedding lithium
Even negative electrode active material, negative electrode active material and anode pole piece II form lithium-ion capacitor.Lithium-ion capacitor production
Process flow is almost the same with common lithium-ion production technology, and process flow is simpler；The embedding lithium technique of negative electrode material is simultaneously not used
Active metal lithium, production process is safe and reliable, while simplifying production technology and equipments requirement；It the characteristics of using micropore copper foil, can
To form uniform embedding cathode of lithium active material in cathode pole piece.
The lithium-ion capacitor making technology process of the invention and lithium ion battery process flow are about the same, safe and simple
List, feasibility are strong, easily realization industrial volume production, have biggish application value.
Detailed description of the invention
Fig. 1 is lithium-ion capacitor internal structure partial schematic diagram,
Wherein 1 is cathode pole piece for anode pole piece I, 2 and 4, and 3 be anode pole piece II, and 5 be diaphragm.
Specific embodiment
Below with reference to specific embodiment, the present invention is further described.But the purposes and mesh of these exemplary embodiments
Be only used to enumerate the present invention, any type of any restriction not is constituted to real protection scope of the invention, it is more non-to incite somebody to action this
The protection scope of invention is confined to this.
Following instance does not form any restrictions to the present invention by taking lamination Soft Roll lithium-ion capacitor as an example.
Embodiment 1:
1, anode pole piece I makes:
Each substance is compared by weight percent: ternary nickle cobalt lithium manganate (LiNi0.5Co0.2Mn0.3O2): conductive carbon black (SP):
Kynoar (PVDF)=94%:3.5%:2.5% is uniformly mixed, and forms stable slurry；Prepared anode sizing agent is equal
Even to be coated on aluminium foil tow sides, aluminium foil both sides reserve sky foil as pole-piece pole-ear position, are used for tab welding, pass through roll-in, mould
Positive plate is made after cutting, made positive plate is placed and is saved under vacuum condition, for use.
2, anode pole piece II makes:
Each substance is compared by weight percent: active carbon: conductive carbon black (SP): carbon nanotube (CNT): Kynoar
(PVDF)=96%:1.0%:1.5%:1.5% is uniformly mixed, and forms stable slurry；Prepared anode sizing agent is uniformly applied
For cloth in aluminium foil tow sides, aluminium foil both sides reserve sky foil as pole-piece pole-ear position, tab welding are used for, after roll-in, cross cutting
Positive plate is made, made positive plate is placed and is saved under vacuum condition, for use.
3, cathode pole piece makes:
Each substance is compared by weight percent: graphite: conductive carbon black (SP): sodium carboxymethylcellulose (CMC): butadiene-styrene latex
(SBR)=96%:1%:1%:2% is uniformly mixed, and forms stable slurry；Prepared negative electrode slurry is uniformly coated on micropore
Copper foil tow sides, copper foil both sides reserve sky foil as pole-piece pole-ear position, tab welding are used for, by being made after roll-in, cross cutting
Made negative electrode tab is placed and is saved under vacuum condition, for use by negative electrode tab.
4, lithium-ion capacitor assembles:
It is assembled by the way of lamination, successively with diaphragm, anode pole piece I, diaphragm, cathode pole piece, diaphragm, anode pole piece
II, diaphragm, cathode pole piece, diaphragm sequence lamination be fabricated to naked battery core, after short-circuit test, through tab welding, aluminum plastic film encapsulation,
Roasting procedure；Fluid injection, electrolyte solute are lithium hexafluoro phosphate, and solvent is ethylene carbonate: methyl ethyl carbonate=1:1；To anode
Pole piece I and cathode pole piece carry out constant-current charge, carry out the pre- embedding lithium of electrochemistry, after the molding of two envelopes, anode pole piece II and cathode pole piece
Form lithium-ion capacitor.The voltage range of the lithium-ion capacitor is 4.1~0V.
Embodiment 2:
By taking lamination Soft Roll lithium-ion capacitor as an example, compared with example 1, the difference is that each substance of anode pole piece II
Quality proportioning is different, and each material mass percentage ratio is active carbon: conductive carbon black (SP): carbon nanotube (CNT): Kynoar
(PVDF)=96.5%:0.8%:1.5%:1.2%, other are all the same.
Embodiment 3:
By taking lamination Soft Roll lithium-ion capacitor as an example, compared with example 1, the difference is that each substance of anode pole piece II
Quality proportioning is different, and each material mass percentage ratio is active carbon: conductive carbon black (SP): carbon nanotube (CNT): Kynoar
(PVDF)=95%:1.5%:2%:1.5%, other are all the same.
Embodiment 4:
By taking lamination Soft Roll lithium-ion capacitor as an example, compared with example 1, the difference is that each substance of anode pole piece II
Quality proportioning is different, and each material mass percentage ratio is active carbon: conductive carbon black (SP): carbon nanotube (CNT): Kynoar
(PVDF)=93%:1.5%:3.5%:2%, other are all the same.
Embodiment 5:
By taking lamination Soft Roll lithium-ion capacitor as an example, compared with example 1, the difference is that each substance of anode pole piece II
Quality proportioning is different, and each material mass percentage ratio is active carbon: conductive carbon black (SP): carbon nanotube (CNT): Kynoar
(PVDF)=90%:2%:5.5%:2.5%, other are all the same.
Embodiment 6: by taking lamination Soft Roll lithium-ion capacitor as an example, compared with example 1, the difference is that anode pole piece I
The quality proportioning of each substance is different, and each material mass percentage ratio is ternary nickle cobalt lithium manganate (LiNi0.5Co0.2Mn0.3O2): it leads
Electrical carbon is black (SP): Kynoar (PVDF)=92%:4.5%:3.5%, other are all the same.
Embodiment 7: by taking lamination Soft Roll lithium-ion capacitor as an example, compared with example 1, the difference is that anode pole piece I
The quality proportioning of each substance is different, and each material mass percentage ratio is ternary nickle cobalt lithium manganate (LiNi0.5Co0.2Mn0.3O2): it leads
Electrical carbon is black (SP): Kynoar (PVDF)=90%:5.5%:4.5%, other are all the same.
Embodiment 8: by taking lamination Soft Roll lithium-ion capacitor as an example, compared with example 1, the difference is that anode pole piece I
The quality proportioning of each substance is different, and each material mass percentage ratio is ternary nickle cobalt lithium manganate (LiNi0.5Co0.2Mn0.3O2): it leads
Electrical carbon is black (SP): Kynoar (PVDF)=96%:2.5%:1.5%, other are all the same.
Embodiment 9: by taking lamination Soft Roll lithium-ion capacitor as an example, compared with example 1, the difference is that cathode pole piece I
The quality proportioning of each substance is different, and each material mass percentage ratio is graphite: conductive carbon black (SP): sodium carboxymethylcellulose
(CMC): butadiene-styrene latex (SBR)=94%:1.5%:1.5%:3%, other are all the same.
Embodiment 10: by taking lamination Soft Roll lithium-ion capacitor as an example, compared with example 1, the difference is that cathode pole piece I
The quality proportioning of each substance is different, and each material mass percentage ratio is graphite: conductive carbon black (SP): sodium carboxymethylcellulose
(CMC): butadiene-styrene latex (SBR)=92%:2%:2%:4%, other are all the same.
Embodiment 11: by taking lamination Soft Roll lithium-ion capacitor as an example, compared with example 1, the difference is that cathode pole piece I
The quality proportioning of each substance is different, and each material mass percentage ratio is graphite: conductive carbon black (SP): sodium carboxymethylcellulose
(CMC): butadiene-styrene latex (SBR)=95%:1.5%:1.5%:2%, other are all the same.
The electrical property of lithium-ion capacitor in examples detailed above is compared below, is summarized as shown in table 1:
| Embodiment | Energy density (Wh/Kg) | Power density (W/kg) |
| Embodiment 1 | 43.8 | 5200 |
| Embodiment 2 | 44.6 | 4950 |
| Embodiment 3 | 40.4 | 5500 |
| Embodiment 4 | 39.1 | 5800 |
| Embodiment 5 | 37.6 | 6300 |
| Embodiment 6 | 42.6 | 5120 |
| Embodiment 7 | 41.8 | 5100 |
| Embodiment 8 | 44.1 | 5240 |
| Embodiment 9 | 43.0 | 5130 |
| Embodiment 10 | 42.4 | 5060 |
| Embodiment 11 | 43.4 | 5160 |
Compared with traditional handicraft, above embodiments are all made of active lithium as lithium source wanted during the manufacturing it is easy,
Safety.
It should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and is not intended to limit protection model of the invention
It encloses.In addition, it should also be understood that, after reading the technical contents of the present invention, those skilled in the art can make the present invention each
Kind change, modification and/or variation, all these equivalent forms equally fall within guarantor defined by the application the appended claims
Within the scope of shield.
Claims (10)
1. a kind of lithium-ion capacitor, including anode pole piece, cathode pole piece, diaphragm, electrolyte and shell, it is characterised in that: institute
Stating anode pole piece includes anode pole piece I, anode pole piece II, and wherein anode pole piece I is to provide lithium source electrode, and anode pole piece I includes
Collector, binder, conductive agent, positive electrode active materials I, anode pole piece II are with capacitive property electrode, the packet of anode pole piece II
Collector, binder, conductive agent, active material are included, cathode pole piece is to be electrolysed with battery performance battery performance, cathode pole piece packet
Collector, binder, conductive agent, active material are included, passes through ingredient, coating, roll-in, cutting preparation with superior pole piece, and successively
Lamination or volume in a manner of diaphragm, anode pole piece I, diaphragm, cathode pole piece, diaphragm, anode pole piece II, diaphragm, cathode pole piece
Around assembling, welds, enters shell, lithium-ion capacitor is made in fluid injection, activation procedure.
2. a kind of lithium-ion capacitor as described in claim 1, it is characterised in that: the anode pole piece I is by collector, anode
Active material, conductive agent, binder composition, wherein positive electrode active materials are preferred lithium nickelate, cobalt acid lithium, LiMn2O4, nickel ternary
Cobalt manganic acid lithium, ternary nickel cobalt lithium aluminate, ferrate-lithium, LiFePO4, iron manganese phosphate for lithium, nickel ion doped, in lithium-rich manganese base material
One kind, the positive electrode active materials, conductive agent, binder ratio be 98~90:6~1.0:4~0.8.
3. a kind of lithium-ion capacitor as claimed in claim 2, it is characterised in that: the anode pole piece II is by collector, work
Property material, conductive agent, binder composition, wherein active material is one in the nano-carbon materials such as graphene, active carbon, porous carbon
Kind, active material, conductive agent, binder ratio be 97~90:7.5~1.5:3.5~0.8.
4. a kind of lithium-ion capacitor as claimed in claim 3, it is characterised in that: the plus plate current-collecting body is non-porous or has a hole
Aluminium foil, with a thickness of 10 μm~20 μm.
5. a kind of lithium-ion capacitor as claimed in claim 4, it is characterised in that: the cathode pole piece is by collector, cathode
Active material, conductive agent, binder composition, wherein negative electrode active material is graphite, carbonaceous mesophase spherules, hard carbon, soft carbon, silicon
One of negative electrode materials such as carbon/silicon oxygen are a variety of, the percentage composition range point of negative electrode active material, conductive agent, binder
It Wei not 97~92:5~0.5:3.5~0.8.
6. a kind of lithium-ion capacitor as claimed in claim 5, it is characterised in that: the negative current collector is micropore copper foil,
With a thickness of 6 μm~16 μm, porosity is 10%~70%, and pore size is 20 μm~130 μm.
7. a kind of lithium-ion capacitor as claimed in claim 6, it is characterised in that: the conduction that the positive and negative electrode pole piece uses
Agent is that conductive carbon black, electrically conductive graphite, carbon fiber, carbon nanotube, graphene and its hybrid conductive slurry etc. are one such or more
Kind.
8. a kind of lithium-ion capacitor as claimed in claim 7, it is characterised in that: the binder is polytetrafluoroethylene (PTFE), gathers
Vinylidene, carboxymethylcellulose sodium, poly- butadiene-styrene latex etc. are one such or a variety of.
9. such as a kind of described in any item lithium-ion capacitors of claim 1-8, it is characterised in that: the diaphragm be polyethylene,
One of polypropylene, polyethylene/polypropylene/polyethylene diagrams.
10. the preparation method of lithium-ion capacitor, characterized by the following steps:
(1) anode pole piece I makes:
By each substance by weight percent than uniformly mixing, stable slurry is formed；Prepared anode sizing agent is uniformly coated on
Aluminium foil tow sides, aluminium foil both sides reserve sky foil as pole-piece pole-ear position, tab welding are used for, by being made after roll-in, cross cutting
Made positive plate is placed and is saved under vacuum condition, for use by positive plate；
(2) anode pole piece II makes:
By each substance by weight percent than uniformly mixing, stable slurry is formed；Prepared anode sizing agent is uniformly coated on
Aluminium foil tow sides, aluminium foil both sides reserve sky foil as pole-piece pole-ear position, tab welding are used for, by being made after roll-in, cross cutting
Made positive plate is placed and is saved under vacuum condition, for use by positive plate；
(3) cathode pole piece makes:
By each substance by weight percent than uniformly mixing, stable slurry is formed；Prepared negative electrode slurry is uniformly coated on
Micropore copper foil tow sides, copper foil both sides reserve sky foil as pole-piece pole-ear position, tab welding are used for, after roll-in, cross cutting
Negative electrode tab is made, made negative electrode tab is placed and is saved under vacuum condition, for use；
(4) lithium-ion capacitor assembles:
Assembled by the way of lamination, successively with diaphragm, anode pole piece I, diaphragm, cathode pole piece, diaphragm, anode pole piece II, every
Film, cathode pole piece, diaphragm sequence lamination be fabricated to naked battery core, after short-circuit test, through tab welding, aluminum plastic film encapsulation, baking
Process；Fluid injection；Constant-current charge is carried out to anode pole piece I and cathode pole piece, carries out the pre- embedding lithium of electrochemistry, after the molding of two envelopes, anode
Pole piece II and cathode pole piece form lithium-ion capacitor.
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